MnFe2O4 has been regarded as a very promising sorbent for mercury emission control in coal-fired power plants because of its high adsorption capacity, magnetic, recyclable and regenerable properties. First-principle calculations based on density functional theory (DFT) were used to elucidate the mercury adsorption and oxidation mechanisms on MnFe2O4 surface. DFT calculations show that Mn-terminated MnFe2O4 (1 0 0) surface is much more stable than Fe-terminated surface. Hg is physically adsorbed on Fe-terminated MnFe2O4 (1 0 0) surface. Hg-0 adsorption on Mn-terminated MnFe2O4 (1 0 0) surface is a chemisorption process. The partial density of states (PDOS) analysis indicates that Hg atom interacts strongly with surface Mn atoms through the orbital hybridization. HgO is adsorbed on the MnFe2O4 surface in a chemical adsorption manner. The small HOMO-LUMO energy gap implies that HgO molecular shows high chemical reactivity for HgO adsorption on MnFe2O4 surface. The energy barriers of Hg-0 oxidation by oxygen on Fe- and Mn-terminated MnFe2O4 surfaces are 206.37 and 76.07 kj/mol, respectively. Mn-terminated surface is much more favorable for Hg-0 oxidation than Fe-terminated surface. In the whole Hg-0 oxidation process, the reaction between adsorbed mercury and surface oxygen is the rate-determining step. (C) 2016 Published by Elsevier B.V.